Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
  • C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers

Definitions

• This invention relates to the synthesis of 1,11-undecanediamine. More specifically, the invention relates to a process for conversion of 7-(5'-aminopentyl)-3,4,5,6-tetrahydro-2H-azepine, hereinafter referred to as Schiff's base (I) and represented by Formula I, ##STR1## and/or 1,11-diaminoundecanol-6, hereinafter referred to as the amino-alcohol (II), and represented by Formula II, ##STR2## to 1,11-undecanediamine by catalytic hydrogenation.
• Schiff's base I
• III 1,11-diaminoundecanol-6
• Formula II amino-alcohol
• the product of the present invention is a very important raw material in synthetic chemical industries, particularly in the polymerization field which includes the manufacture of synthetic fibers or resins.
• process (i) complicated procedures are required in order to provide the necessary starting materials.
• process (ii) a quantitative amount of costly hydrazine (or of a derivative) is consumed.
• process (iii) an unsatisfactorily low yield of the desired diamine is produced and at a rather slow reaction rate.
• This process also involves severe reaction conditions such as highly elevated pressures and temperatures, e.g., 100 atmospheres and 170° C.
• acetic acid is inevitably accompanied by many deterrents of commercial utilization; the corrosive properties of acetic acid cause many difficulties, and the presence of a large quantity of the acidic solvent makes it complicated to isolate the alkaline product. Therefore, none of the foregoing processes has yet achieved commercial exploitation, so far as we are aware.
• Schiff's base (I) can be selectively hydrogenated to 1,11-undecanediamine at a relatively high reaction rate under specific hydrogenation conditions, as described below, in which particular diluent and inorganic acid employed, and hydrogenation catalyst provided are essential.
• 1,11-undecanediamine of high quality can be prepared in good yield.
• the process of the present invention is effected in a diluent comprising aqueous sulfuric acid containing at least about 1.2 moles of sulfuric acid per mole of the Schiff's base (I) and/or the amino-alcohol (II) in the presence of a hydrogenation catalyst containing at least one component selected from the group consisting of metals of the platinum group and rhenium.
• Reaction conditions other than those of the present invention fail to accomplish the remarkable results attained by the present invention. Indeed, it has been reported in an operative example of the above mentioned Japanese Patent Publication No.
• 1,11-undecanediamine can be produced from Schiff's base (I) and/or the amino-alcohol (II) in one step.
• the reaction process is believed to proceed in accordance with the following equations: ##STR4##
• amino-alcohol (II) is accordingly an intermediate in the preparation of the product.
• the Schiff's base (I) is in equilibrium with 1,11-diaminoundecanone-6, as shown in the foregoing reaction diagram, in the presence of water. These compounds in equilibrium afford salts with acidic compounds such as sulfuric acid, phosphoric acid, hydrogen chloride, carbonic acid or carbon dioxide, or carboxylic acids.
• the salts can be isolated as salts of 1,11-diaminoundecanone-6 with most of the acidic compounds except carbonic acid or carbon dioxide; with those compounds a mixture of the carbamates represented by Formula IV, ##STR5## is isolated.
• the Schiff's base (I) is produced by thermolysis of ⁇ -caprolactam, ⁇ -aminocaproic acid, or an oligomer or polymer thereof, in the presence of a hydroxide or oxide of an alkali metal or alkali earth metal such as lithium, calcium, etc.
• the amino-alcohol (II) another starting material is known to be produced by chemically reducing the Schiff's base (I) with an alkali metal hydroxide in a lower aliphatic hydroxy compound such as methanol, ethanol, etc. (U.S. Pat. No. 3,412,156). It can also be produced by partial catalytic hydrogenation of the Schiff's base (I) as disclosed here.
• the process of the present invention can be practiced in a diluent of aqueous sulfuric acid containing at least 1.2 moles of sulfuric acid per mole of the Schiff's base (I) and/or the amino-alcohol (II) in the reaction mixture.
• the reaction proceeds even when smaller amounts of sulfuric acid are used, but the products of side reactions such as the perhydroazepine (III) and/or the amino-alcohol (II) may be predominant in some cases.
• the upper limit of the amount of sulfuric acid can be quite high, e.g., ten or more moles per mole of the starting material, but no particular advantages are obtained in such a case. Therefore, from a practical viewpoint, the amount of sulfuric acid employed in the reaction mixture may be in an amount of from about 1.2 to 10 moles preferably in an amount of from about 1.5 to 8 moles, and more preferably about 2 to 5 moles per mole of Schiff's base (I) and/or the amino-alcohol (II) employed in the reaction mixture.
• a bisulfate such as ammonium bisulfate, sodium bisulfate or potassium bisulfate, etc.
• a bisulfate such as ammonium bisulfate, sodium bisulfate or potassium bisulfate, etc.
• the concentration of aqueous sulfuric acid in the reaction mixture is an important factor in the process of the invention.
• the concentration of the aqueous sulfuric acid used is not narrowly critical and can vary over a wide range. In general, at relatively higher concentrations, e.g., at concentrations as high as 70 weight percent and higher based on the total quantity of water and sulfuric acid, the rate of hydrogenation of a starting material may be extremely slow. On the other hand, at lower concentrations, the intermediate of the desired reaction, the amino-alcohol (II) may remain increasingly unreacted when starting from the Schiff's base (I), and therefore it is desirable to employ higher temperatures and/or a longer reaction time. At concentrations below 2 weight percent, the rate of desired product formation becomes quite slow.
• a suitable range of concentration of aqueous sulfuric acid is from about 2 weight percent to about 60 weight percent, preferably from about 5 weight percent to about 50 weight percent, based on the total quantity of water and sulfuric acid in the reaction mixture.
• the invention is carried out in the presence of a hydrogenation catalyst having at least one component selected from the group consisting of metals of the platinum group and rhenium.
• Metals of the platinum group include ruthenium, rhodium, palladium, osmium, iridium, and platinum. Among these metals, rhenium, ruthenium, rhodium, osmium, iridium and platinum are preferred, when starting from the Schiff's base (I). Further, an increased reaction rate and/or higher conversion to the desired product can be obtained in the presence of ruthenium, osmium or iridium. The combined use of two or more of these metals is also effective.
• the hydrogenation catalyst may be used in optional forms, such as sponge, fine powder, colloid and supported form.
• Catalyst supports employed are, for example, silica, alumina, titania, charcoal, niobium pentoxide, tungsten trioxide, molybdenum trioxide, zeolites, asbestos, porous glass, silicon carbide, zirconia, barium sulfate and the like, and mixtures thereof as well as other suitable stable materials.
• the catalytic activity in reactions according to this invention may be promoted in the presence of a co-catalyst containing at least one component selected from the group consisting of metals of tungsten and molybdenum, when starting from Schiff's base (I).
• Illustrative co-catalysts which are generally suitable in the practice of desirable embodiments of the invention include, for example, metals or metal powders of tungsten or molybdenum, alloys containing tungsten or molybdenum, compounds of tungsten or molybdenum such as molybdic acid or its salts; tungstic acid or its salts; heteropolyacids or their salts such as phosphotungstic acid, phosphomolybdic acid or salts of either; tungsten oxide; molybdenum oxide; tungsten hexacarbonyl; molybdenum hexacarbonyl; and others.
• the quantity of co-catalyst employed is not narrowly critical and can vary over a wide range.
• the co-catalyst component may be used in an amount of from about 0.01 to 100 parts preferably in an amount of from about 0.1 to 50 parts, by weight, based on the amount of the active metallic component of the hydrogenation catalyst.
• the operative temperatures which may be employed can vary over a wide range of elevated temperatures.
• the process can be conducted at a temperature in the range of about 80° C. and upwards to approximately 350° C. and higher.
• the rate of reaction to form the desired product becomes markedly slow, and the formation of the intermediate of the reaction, the amino-alcohol (II) when starting from the Schiff's base (I) may be predominant.
• the activity of the catalyst used tends to become unstable. It is readily appreciated that the reaction temperature will be influenced, to a significant extent, by the concentration and amount of aqueous sulfuric acid, the reaction time and other factors.
• Suitable operating temperatures can be between about 100° C. and about 300° C., and desirably from about 120° C. to about 250° C.
• the process can be effected suitably over a wide range of hydrogen partial pressures of from about 1 to about 300 kilograms per square centimeter absolute.
• the pressure utilized will depend upon the reaction rate and the investment costs associated with erecting chemical plants with high pressure facilities.
• a preferred range of hydrogen partial pressures is from about 5 to about 150 atmospheres.
• the hydrogen employed need not be pure, but it can be diluted with inert gases such as nitrogen, argon, methane, etc.
• the process can be executed in a batch, semi-continuous, or continuous fashion.
• the reaction can be conducted in a single reaction zone or a plurality of reaction zones, in series or in parallel, or it may be conducted intermittently or continuously in an elongated tubular zone or series of such zones.
• Catalysts may be introduced initially into the reaction zone batchwise, or may be continuously or intermittently introduced into such zone during the course of the synthesis reaction.
• Means to introduce and/or adjust the materials responsible for the reaction, either intermittently or continuously, into the reaction zone during the course of the reaction can be conveniently utilized in the process especially to maintain the desired molar ratios of, and the partial pressures of, the materials.
• Isolation and purification of the desired product can be achieved by methods well-known in the art such as neutralization, concentration, phase-separation, extraction, crystallization, recrystallization, distillation, combinations thereof, and the like.
• Example 17 the catalyst was prepared by mixing 0.84 g of ruthenium trichloride monohydrate, 0.21 g of palladium chloride and 66.7 g of "Snowtex N-20" (silica sol obtained from Nissan Kogyo Co., containing 30% SiO 2 ), evaporating the water to dryness on a hot bath in vacuo. The product was reduced in a stream of hydrogen at 150° C. for 5 hours, then allowed to stand under an atmosphere of ammonia for several hours at ambient temperature, then washed with water, and further reduced in a stream of hydrogen at 150° C. for 5 hours. The product was the desired catalyst containing 5 percent by total weight ruthenium and palladium in a ratio of 8:2.
• Example 18 the catalyst was prepared in a manner similar to that set forth in Example 17 by mixing ruthenium trichloride, rhodium trichloride and silica sol in amounts sufficient to provide a final catalyst containing 5 percent by total weight of ruthenium and rhodium in a ratio of 8:2.
• This example was prepared in a manner similar to that set forth in Example 2, using 0.5 g of 1,11-diaminoundecanol-6, 50 mg. of a 5% ruthenium-on-silica gel catalyst, and 3 ml. of 24% sulfuric acid. The reaction was carried out at a temperature of 150° C. and under pressure of 10 atm. After a reaction period of 3.5 hours, the reaction mixture was subjected to analysis by means of a gas chromatograph. The analysis showed that a 96% yield of 1,11-undecanediamine had been produced.
• Example 34 a yield of about 30% 1,11-diaminoundecanol-6 was detected.
• Example 49 the catalyst is the same as that used in Example 17.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)

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Citations (6)

• 1976
  • 1976-10-22 JP JP12629976A patent/JPS5353604A/ja active Granted
• 1977
  • 1977-10-19 DE DE2746930A patent/DE2746930C2/de not_active Expired
  • 1977-10-21 FR FR7731816A patent/FR2368463A1/fr active Granted
  • 1977-10-21 GB GB43818/77A patent/GB1534636A/en not_active Expired
  • 1977-10-25 US US05/845,401 patent/US4172848A/en not_active Expired - Lifetime

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Non-Patent Citations (2)

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